Composition and process for finishing woolen textiles



Patented Dec. 2, 1952 CUMPOSITION AND PROCESS FOR FINISHING WOOLEN TEXTILES George L. Royer, North Plainfield, and Chester A.

Amick, Bound Brook, N. J assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application May 1, 1951, Serial No. 224,070

3 Claims.

This invention relates to the finishing of woolen textiles such as woolen yarns and cloth, raw wool and the like, as well as wool-containing textiles in which the wool is blended with other fibers such as the cellulosic fibers. The invention includes the application to woolen textiles of novel finishing compositions capable of imparting thereto combined shrinkage control and insecticidal properties.

It has been the practice for many years to apply mothproofing or insecticidal materials, including the inorganic and organic fluorides and silicofiuorides to woolen textiles. Within recent years it has become the practice to control the shrinkage of woolen textile materials by impregnating them with a solution of a water-dispersible alkylated or alcohol-reacted methylol melamine followed by drying the impregnated textiles and heating them for a short time in order to cure the resin to a water-insoluble condition as described in U. S. Reissue Patent No. 22,566.

The present invention is directed to a textile finishing composition which, when impregnated into woolen textiles of the type described above, will impart both complete mothproofin and a complete shrinkage control upon a single application. The composition of our invention is made up of an aqueous solution of water-soluble methylated or otherwise alkylated methylol melamine having triethanolamine silicoiiuoride dissolved therein in the proportions hereinafter described.

The following are the principal advantages of the composition of our invention. In addition to its known function in controlling shrinkage, the methylated methylol melamine also prevents loss of the triethanolamine silicofiuoride upon laundering the treated textiles. Furthermore, complete penetration of the woolen textiles both by the mothproofing agent and by the methylated methylol melamine is obtained. Moreover, upon drying the impregnated textiles and heating in the usual manner (as described in Reissue Patent No. 22,566) the fluoride remains suspended in the resin; a relatively large proportion of fluoride, with respect to the quantit of resin, can therefore be applied and retained in a wash-fast condition. It is a surprising advantage of our invention that a quantity of triethanolamine silicofluoride of about 0.5% in about based on the dry weight of the textiles, can be insolubilized and made laundry-resistant on the textiles with a quantity of methylated methylol melamine of about 2-15%, also based on the dry weight of the even though this mothproofing agent is normally water-soluble; as is apparent from Example 1 hereinbelow, excellent results have been obtained with a. textile-finishing bath containing approximately 13% by weight of methylated methylol melamine and a smaller amount of triethanolamine silicofluoride in aqueous solution.

Furthermore, the mothproofing action of the triethanolamine silicofluoride is not impaired by its presence in the textiles as the internal phase of a resin-silicofluoride mixture. This is clearly shown by the tests reported in the following examples. Our invention therefore presents the important advantages of (1) application to textiles by a one-bath process; (2) complete shrinkage control combined with complete mothproofing and (3) wide range of proportions of triethanolamine silicofluoride to methylated methylol melamine while still retaining the advantages of the invention.

Suitable alkylated methyiol melamines are ethylated or ethanol-reacted trimethylol melamine and butylated trimethylol melamine, preferably applied from aqueous solutions containing organic solvents, but the preferred resinous material is water-soluble methylated methylol melamine. This material is prepared by the following process.

One mol of melamine is mixed with 3.3 mols of aqueous 37% formaldehyde previously adjusted to a pH of approximately 8.0, the temperature being raised to C. and maintained at this point until a clear solution is obtained. The solution is then immediately cooled and allowed to set and the mass is broken into small pieces and dried by circulating warm air at a temperature not exceeding 55 C. The resulting dried powder is alkylated by admixture with twice its weight of 95% methanol containing 0.5% of oxalic acid crystals, based on the weight of the methylol melamine. The mixture is heated to 70 C. and held at this temperature for approximately 15 minutes, or until a clear solution is obtained, whereupon it is immediately neutralized by the addition of sufiicient sodium hydroxide solution to raise the pH to approximately 9.0. The neutralized reaction mixture is then evaporated to solids under reduced pressure so that the temperature does not rise above 50 C.

The textile-finishing compositions of the present invention, at the dilutions used for application, contain the methylated methylol melamine dissolved therein to a strength roughly equivalent to the percent of resin desired in the textiles toether with the amount of silicoiiuoride desired for insecticidal purposes. The triethanolamine silicofluoride may be dissolved in the aqueous methylated methylol melamine solution or it may be added thereto as a separately prepared solution in water. It is an important advantage of the invention that the triethanolamine silicofiuoride, being both water-soluble and non-ionic, does not tend to precipitate the methylated methylol melamine from the bath or otherwise reduce the bath-stability.

It is well known that a curing accelerator for the alkylated methylol melamine such, for example, as diammonium hydrogen phosphate should be used in amounts of about 3% based on the weight of the alkylated methylol melamine. The water-soluble triethanolamine silicofiuoride can be used to replace this or other curing accelerators without interfering in any way with its insecticidal properties. This is true even when the impregnating bath is made alkaline with a 1 volatile base such as ammonia, triethanolamine and the like.

same wool flannel treated with triethanolamine silicofluoride solution containing no resinous binder, followed by washing. Th triethanolamine silicofluoride was so completely removed by washing that there was substantially no protection against the carpet beetle larvae, and the shrinkage figure was of course substantially identical with that of the original untreated fabric.

Example 2 The procedure of Example 1 was followed but the amount of resin, the amount of the triethanolamine silicofiuoride and, in certain instances, the catalyst (diammonium hydrogen phosphate) were varied as shown in the following table. In two instances no catalyst as such was added but the triethanolamine silicofluoride acted as its own The following specific examples are illustrative catalyst. The results obtained were as follows r Shrinkage After Tummcut' Qfigg nrcent on Weight of Droppings (Grams) Five Washes,

Percent TEA Unwashed Wool After Washes I Resin Silico- NHmHPo X3? f P fluonde Untreated Treated Untreated Treated 12. 8 4. 10.5 0.0 21.4 2. 6 1. 6 0. 8 l0. 0 3. 0. 4 10.5 2.0 '21. 4 8. 2 0.0 4. 7 ,10. 0 1. 3 10. 5 0. 2 21. 4 3. 1 1. 0 0. 0 12. 8 8. 0 0. 4 10. 5 0. 0 21. 4 9. 0 0. 0 0. 0 12. 8 16. 0 0.4 10.5 0. 0 21. 4 2. 5 0. 0 0.0 6. 4 O. 7 0.2 10. 5 2. 5 21. 4 4. l 10. 3 l1. 6 6.4 0.7 0.2 9.1 1.1 20.6 2.7 1.7 1.9

1 Control. No treatment.

1 W001 pretreated with 11:02 (American Dyestuii Reporter 33, 329 (1944).

of the results obtained in finishing woolen textiles by the process of the present invention.

Example 1 A textile-finishing bath was prepared by adding 15 cc. of triethanolamine silicofiuoride dissolved in about 150 cc. of water to a solution of grams of methylated methylol melamine, prepared as described above, in 140 cc. of water. Two 12" x 12 pieces of wool flannel, weighing about 34.5 grams, were thoroughly wet out in the treating bath and then passed through padder rolls set to retain a weight of bath solution equal to about 95% of the weight of the cloth. The pieces were air-dried at about 80 C. after which they were heated 9 minutes at 140 C. to cure the resin. One of the pieces was then subjected to five shrinkage wash tests, using the method described in the 1943 Year Book of the American Association of Textile Chemists and Colorists, pages 223 and 226. The shrinkage of the original untreated fabric during five washings was about 40% in the warp and 40% in the filling. The treated piece showed 1.6% shinkage in the warp and 0.8 in the filling.

The washed and unwashed treated pieces and the washed and unwashed untreated pieces were then exposed to black carpet beetle larvae for two weeks, using the method of damage evaluation based on the corrected weight of droppings as described in fSoap and Sanitary Chemicals, August 1942 (vol. 18, No. 8), pages 95-99. The unwashed, untreated piece showed 10.5 mgs. of droppings, whereas the unwashed, treated pieces showed 0.0 mgs. of droppings. The washed, untreated piece showed 21.4 mgs. of droppings, whereas the washed, treated piece showed only 2.6 mgs. of droppings.

These exposures to black carpet beetle larvae were made in comparison with other pieces of the The above table indicates that in every instance protection was obtained by the use of the triethanolamine silicofluoride.

It will also be observed that 6.4% of the resin on regular wool is insufficient to give good shrinkage control, but if the wool is given a prior treatment with hydrogen peroxide by a commercially accepted standard procedure, such as that given in the American Dyestuff Reporter, volume 33, page 329, July 1944, the shrinkage control is appreciably improved.

This is a continuation-in-part of our copending application Serial Number 610,665, filed August 13, 1945, which has issued as Patent No. 2,555,277.

What we claim is:

1. A textile-finishing composition for simultaneously shrinkproofing and mothproofing woolen textiles which comprises an aqueous solution of between 2 and 15 parts by weight of methylated methylol melamine and between 0.5 and 10 parts by weight of triethanolamine silicofluoride.

2. A textile-finishing composition for simultaneously shrinkproofing and mothproofing woolen textiles which comprises an aqueous solution of between 0.5 and 10 parts by weight of triethanolamine silicofiuoride for each 13 parts by weight of methylated methylol melamine.

3. A textile-finishing composition for simultaneously shrinkproofing and mothproofing woolen textiles which comprises an aqueous solution of between 2 and 15 parts by weight of methylated methylol melamine and a smaller quantity of triethanolamine silicofluoride amounting to between 0.5 and 10 parts by weight.

GEORGE L. ROYER. CHESTER A. AMICK.

No references cited. 

1. A TEXTILE-FINISHING COMPOSITION FOR SIMULTANEOUSLY SHRINKPROOFING AND MOTHPROOFING WOOLEN TEXTILES WHICH COMPRISES AN AQUEOUS SOLUTION OF BETWEEN 2 AND 15 PARTS BY WEIGHT OF METHYLATED METHYLOL METLAMINE AND BETWEEN 0.5 AND 10 PARTS BY WEIGHT OF TRIETHANOLAMINE SILICOFLUORIDE. 